Herbicidal pyridine derivatives and their salts of 3-(aminooxoacetyl)-2-(2-imidazolin-2-yl)

ABSTRACT

The present invention relates to new 3-(aminooxoacetyl)-2-(2-imidazolin-2-yl)pyridines and their salts, having herbicidal activity.

TECHNICAL FIELD

The present invention relates to a novel 3-(aminooxoacetyl)-2-(2-imidazolin-2-yl)pyridine and their salts, having a herbicidal activity.

BACKGROUND ART

The imidazolinone herbicides, a potent class, have publicly known and until recently, British patent No. 2,174,395 discloses the compounds having the following formula (A). ##STR1## Wherein:

R¹ is C₁ -C₄ alkyl;

R² is C₁ -C₄ alkyl or C₃ -C₆ cycloalkyl;

B is CO₂ R³, CONHR⁶, CHO, CH₂ OH, COCH₃, COC₆ H₅, CN, CH₃, CH═NOH, CH₂ COOH, CONHOH, CHROH, CH₂ CH₂ COOH, ##STR2## (wherein, R³ is hydrogen, dialkylimino, substituted alkyl, alkenyl or cation, R⁶ is hydrogen, hydroxy or alkenyl) A is hydrogen, COR⁴, SO₂ R⁵, etc.

The above patent introduces many a herbicidal compounds, but they have recognized a disadvantage in that except for soybean, such compounds failed to exert an effective selectivity of herbicidal activity as herbicide.

Also, such imidazolinone compounds are specified in the following patents, say, German Patent No. 2,833,274, U.S. Pat. Nos. 4,824,466/4,851,021/4,824,474, European Patent No. 41,623/298,029/322,616.

However, the current situation is that the undesirable vegetation should be controlled so as to improve the growth of useful crops such as corn, rice, cotton, wheat, and soybean. The failure to check the weed growth in such useful crops may bring about significant losses to farmers and to consumer as well. Thus, the continuous research to develop more effective products should be required for a good harvest.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to novel compounds demonstrating a herbicidal activity and to agriculturally suitable compositions thereof, and a method of their uses as general and/or selective preemergent and/or postemergent herbicides or plant growth regulants.

More specifically, said compounds demonstrating a herbicidal activity are 3-(aminooxoacetyl)-2-(2-imidazolin-2-yl)pyridine having a following stucture of general formula(I). ##STR3## wherein,

R¹ is C₁ -C₄ alkyl;

R² is C₁ -C₄ alkyl, C₃ -C₅ cycloalkyl or C₁ -C₄ alkyl optionally substituted with 1-4 fluorine;

R³ is hydrogen, C₁ -C₃ alkyl, C₁ -C₃ alkyl optionally substituted with substituents contained in the following group I, C₂ -C₄ alkenyl or C₂ -C₄ alkynyl;

R⁴ is the same as R³ ; or phenyl, benzyl, pyridyl, furanyl, thiophenyl, benzofuranyl, dihydrobenzofuranyl, benzothiophenyl, dihydrobenzothiophenyl, indolyl, indolinyl, optionally substituted with 0-3 same or different substituents selected from the substituents contained in group II ; and when taken together, connecting R³ and R⁴, a 3-7 membered ring may be formed, which may contain 0-3 double bonds or 0-3 O, N, SOn(n=0-2);

W is O or S;

X is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkoxyalkyl, or halogen;

Y, Z are each hydrogen, halogen, C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxyalkyl, C₁ -C₆ alkylthio, phenoxy, C₁ -C₆ haloalkyl, C₁ -C₆ alkylamino, C₁ -C₆ alkylsulfonyl or phenyl optionally substituted with one C₁ -C₄ alkyl, C₁ -C₄ alkoxy or halogen; and when taken together, a 5-6 membered ring may be formed in which may contain O,N,S, double bonds or--(CH₂)_(n) --, (n=0-4);

A is hydrogen or --COR⁵ (where R⁵ is hydrogen, methyl or CH₂ Cl); when A is hydrogen, tautomeric isomer may exist;

Group I contains hydroxy, alkoxy, haloalkoxy, cyano, --CO₂ R⁶ (where R⁶ is hydrogen, alkyl, alkenyl, or alkynyl), alkylthio, alkylsulfonyl, phenylthio, phenylsulfonyl, haloalkylthio, alkenoxy, alkoxy, --NR⁶ R⁷ (where R⁶, R⁷ are each hydrogen, alkyl, alkenyl or alkynyl or R⁶, R⁷ may form a ring), phenyl, or phenoxy;

Group II contains group I substituents, halogen, nitro, haloalkyl, alkoxyalkyl, alkyl, alkenyl, alkynyl, alkylthioalkyl, --COR⁸ (where R⁸ is hydrogen, alkyl or phenyl) --CO₂ R⁹ (where R⁹ is hydrogen or alkyl), --SO₃ R¹⁰ (where R¹⁰ is hydrogen or alkyl), --SO₂ NR⁶ R⁷,--CONR⁶ R⁷ (R⁶,R⁷ are the same as above), or ##STR4## (where n, m are an integer of 1-3, D is a single bond or double bond, O, S, SO₂, NCH₃).

A preferred group of 3-(aminooxoacetyl)-2-(2-imidazolin-2-yl)pyridine compounds having the formula shown as above(I), wherein R¹ is methyl, R² is methyl, ethyl, isopropyl or cyclopropyl; W is oxygen; A is hydrogen, X is hydrogen, Y, Z is each hydrogen, C₁ -C₆ alkyl or C₁ -C₆ alkoxy, and when Y and Z are taken together, YZ is --(CH₂)₄, --CH═CH--CH═CH--, or --O(CH₂)₃ --, and R³ is hydrogen or C₁ -C₂ alkyl, R⁴ is C₁ -C₂ alkyl optionally substituted with 0-2 substituents selected from halogen, hydroxy, alkoxy, alkylthio, amino, phenyl, phenoxy;

C₂ -C₆ alkenyl, C₂ -C₆ alkynyl, or phenyl optionally substituted with 0-3 same or different selected from substituents contained in the above group II, when taken together, connecting R³ and R⁴, a 3-7 membered ring may be formed, which may contain 0-3 double bonds or 0-3, O, N, SOn(n=0-2);

A more preferred group of 3-(aminooxoacetyl)-2-(2-imidazolin-2-yl)pyridines, wherein A and X is each hydrogen, Y is hydrogen, C₁ -C₂ alkyl or C₁ -C₂ alkoxy, Z is hydrogen, R¹ is methyl, R² is isopropyl, R³ is methyl or ethyl, R⁴ is benzyl, phenyl, or phenyl substituted with 1-3 substituents selected from C₁ -C₆ alkyl, phenoxy, C₁ -C₆ alkoxy, halogen, haloalkyl, C₁ -C₆ alkylthio, C₁ -C₆ alkylsulfone C₁ -C₆ dialkylamino, or those where --NR³ R⁴ is ##STR5##

Among the definitions according to the present invention, the following terms have the following meanings:

a) "Alkyl" used either alone or in compound words such as "alkylthio" or "haloalkyl", etc. denotes straight chain, or branched alkyls within six carbon atoms.

b) "Alkenyl" denotes straight chain or branched alkenes within six carbon atoms.

c) "Alkynyl" denotes straight chain or branched alkynes within six carbon atom.

d) "Alkoxy" denotes groups of O-alkyls defined as above.

e) "Halogen" denotes either alone or in compound words such as haloalkyl denotes fluorine, chlorine, or bromine.

As a useful herbicide, said 3-(aminooxoacetyl)-2-(2-imidazolin-2-yl) pyridine compounds and their salts of the present invention may be used in cultivating soybean, corn, wheat, barley, rice, and cotton. The salts of said compounds can be prepared as an acid-addition salt or an alkali, alkaline earth metal or quaternary amine salts.

Compounds of the present invention can be prepared by reactions as described in hereinbelow. The compounds of general formula(I) can be obtained by acylating the compounds of formula(II), when neither of R³ or R⁴ is hydrogen, can be prepared as shown in Reaction(1) ##STR6##

From the above reaction(1), BuLi and LDA are preferably used as a strong base, possibly at the temperature of -78°˜30° C.

The synthesis method in the compound of said general formula(II) is publicly known, and its synthesis is available by Korea Patent Publication No. 85-1817 and Germany Patent DE No.2,833,274/3,121,736.

If R³ is hydrogen, the manufacture of said compound should be preferably made available by protecting this functional group under the following reaction(2). ##STR7##

When there is a substituent of hydroxy having active hydrogen in R³ or R⁴ from the above reaction, the systhesis is made available by protecting the substituent under the reaction(1) or reaction(2).

Also, the novel compound of the present invention may be synthesized by the following reaction(3), wherein n=the fixed number of 1˜6, R³ is hydrogen or has a substituent of hydroxy. ##STR8##

If R³ and R⁴ is each hydrogen, the manufacture of said compound should be preferably made available by protecting the amino functional group under the following reaction(4). ##STR9##

Meantime, the manufacture of general formula(III) used in said reaction(1) may be made available by reacting with oxalic acid ester and amine as do in the following reaction(5). ##STR10##

Also, the manufacture of said general formula(IV) and (V) may be made available by the following reaction(6) and (7). ##STR11##

The manufacture of said general formula(VI) may be made available by the existing method, and the manufacture of said general formula(VIII) may be made available by the following reaction(8). ##STR12##

The compounds of said general formula(I) of the present invention specify the following materials:

3-(N-methyl-N-3-fluorophenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2 -yl)-5-methylpyridine

3-(N-methyl-N-3-chloro-4-methoxyphenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2 -imidazolin-2-yl)-5-methylpyridine

3-(N-methyl-N-3,5-dimethylphenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2 -yl)-5-methylpyridine

3-(N-methyl-N-4-n-butylphenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2 -yl)-5-methylpyridine

3-(N-methyl-N-4-t-butylphenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2 -yl)-5-methylpyridine

3-(N-methyl-N-4-phenoxyphenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2 -yl)-5-methylpyridine

3-(N-methyl-N-3-chlorophenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2 -yl)-5-methylpyridine

3-(N-methyl-N-4-cyclohexylphenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2 -yl)-5-methylpyridine

3-(N-methyl-N-4-dimethylaminophenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2yl)-5-methylpyridine

3-(N-methyl-N-3-trifluoromethylphenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2 -imidazolin-2-yl)-5-methylpyridine

3-(N-methyl-N-3,4-dichlorophenyl-aminooxoacetyl)-2(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2 -yl)-5-methylpyridine

3-(N-methyl-N-4-trifluoromethylphenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2 -imidazolin-2-yl)-5-methylpyridine

3-(N-methyl-N-3-methyphenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl )-5-methylpyridine

The above-manufactured compounds of said general formula(I) are used, in various forms of solutions and powders having herbicidal compositions, to the soil containing plant's leaf or plant-breeding part. The dosage forms available are wettable powder, flow concentrates, emulsifiable concentrates, and granules.

According to the present invention, the wettable powder is homogeneously dispersed in water; in addition to the active composition, diluent, and non-toxic material, said wettable agent is manufactured by the following materials: polyoxyethylated alkylphenols, polyoxyethylated fatty alcols, alkyl or alkylphenyl sulfonates. The dispersing agent includes sodium lignin sulfonate, sodium 2,2'-dinaphthylmethane-6,6' disulfonate, sodium dibutyl naphthalene sulfonate, or sodium oleil-methyltauride. Such agents are manufactured by the existing method by pulverizing and mixing the ingredients.

The flow concentrates may be manufactured by mixing/melting the active ingredients into non-toxic organic solvent(e.g., butanol, cyclohexanol, DMF, xylene, or high boiling aromatics, or hydrocarbons), together with any one or more emulsifiers.

As an usable emulsifier, calcium alkylsulfonates includes calcium dodesylbenzenesulfonate or non-ionic emulsifier includes fatty acid polyglycolesters, alkylaryl polyglycolethers, fatty alcol polyglycolethers, propyleneoxide, ethyleneoxide polymers, fattyalcohol, propyleneoxide ethyleneoxide polymers, alkylpolyglocolethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, or polyoxyethylene sorbitol esters.

Also, a powdering agent may be manufactured by pulvering the active ingredient with talc of micropulverized solid and natural clay(e.g., kaolin, bentonite, pyrophilite, or siliceous earth).

And a granular agent may be manufactured either by spraying the active ingredient on inactive adsorbent in granular form or by adsorbing the active flow concentrates on the surface of intermediates, say, sand, kaolinites.

The usable adsorbent includes polyvinyl alcol, sodium polyacrylate or mineral oils.

The herbicides of general formula(I) in the present invention may be manufactured by the existing method of fertilizer-granule agent, and if necessary, they may also be manufactured by the mixture of fertilizer.

The preparations containing aforementioned active ingredients may , if necessary, contain wettable agents, dispersing agents, emulsifiers, impregnating agents, solvents, fillers, intermediates, etc. For the actual appication, the flow concentrates in a commercial form may be used by appropriate dilution.

For example, the wettable powder or emulsifiable concentrates is used by dilution, while powdering/granular/ spraying solution, inactive materials, are not diluted.

Also, the flowable liquid is composed of the following: active ingredient of 30˜50 wt %, gelator of 1˜3 wt %, dispersing agent of 1˜5 wt %, alcohol of 0.1˜3 wt %, and water of 40˜60 wt %. The prevailing method of manufacturing the flowable liquid is based upon the following formula: in proportion to the active ingredient of about 40 wt %, gelator(e.g., bentonite) of about 2 wt %, dispersing agent(e.g., lignosulfate), polyethylene alcohol of 1 wt %, and water of 54 wt %.

Also, the prevailing method of manufacturing the concentrated emulsifying liquids is based upon the following formula: after dissolving the active ingredient of about 5˜25 wt % into N-methylpyrrolidone, isoporone, butylcellosolve, methylacetate in about 65˜90 wt %, some non-ionic surfactant(e.g., alkyloxy polyethoxy alcohol) of about 5˜10 wt % is dispersed into said liquids. When said concentrated liquids are used, they are dispersed into water to make the spraying solution.

In case the compounds of the present invention are to be used as the herbicide containing a soil-treating agent, they may be used by manufacturing a granular agent; to manufacture said agent, the active ingredient is dissolved into some solvent(e.g., methylene chloride and N-methylpyrrolidone) and said formed solution is sprayed to granular carries such as powder of corn stalk, sand, attapulgite, and kaolin. In general, the above manufactured granular agent contains the active ingredient of about 3˜20 wt % and the granular carrier of about 97˜80 wt %.

Meantime, the compounds of general formula(I) of the present invention are the most effective herbicide in controlling one-year weed, perenial plant, mono- or bicotyledonous plant.

Also, said compounds is quite effective in eliminating the weeds growing in the dry/humid soil areas only. They are used as underwater herbicides and if said compounds, in a ratio of about 0.06˜10 kg/ha, are given to plant's leaves, soil, or the breeding parts such as tuber, rhizome, or ladix, the plant may be eliminated successfully and effectively.

Moreover, surprisingly, it is found that various kinds of compounds of general formula(I) demonstrate their selective herbicidal effect according to the kinds of plant eliminated, when they are given to plant's leaves, or soil, in a low ratio. It is also noted that said compounds may be widely used as pre-emergent or as post-emergent.

However, it does not mean that said compounds of general formula(I) are non-selective. Especially, certain compounds are selective in soybean, wheat, barley, corn, rice, and cotton, while other compounds are said to be effective as growth-inhibitors against plant.

As above, the novel compounds of the present invention may be used not only as effective herbicides, but also as growth-modulators for inhibiting the plant's growth. The applicable amount of said compounds is decided based upon various considerable factors.

For example, the following factors should be considered; kinds of plants, controlled type of weeds, climate, weather, dosage forms, applicable methods, quantity of leaf. A low amount is preferably used in the following cases; a) soil having less content of organic material b) the transformation inplant growth or short-term duration should be required.

The following Examples illustrate ways in which the principle of this invention has been applied, but are not to be construed as limiting its scope.

    ______________________________________                                         acetochlor     bromacil      clethodim                                         acifluofen     bromoxynil    clomazone                                         acrolein       butachlor     cloproxydim                                       alachlor       buthidazole   clopyralid                                        ametryn        butralin      CMA                                               amitrole       butylate      cyanazine                                         AMS            cacodylic acid                                                                               cycloate                                          asulam         CDAA          cycluron                                          atrazine       CDEC          cyperquat                                         barban         chloramben    cyprazine                                         benefin        chlorbromuron cyprazole                                         bensulfuron methyl                                                                            chlorimuron ethyl                                                                            cypromid                                          bensulide      chloroxuron   dalapon                                           bentazon       chlorporpham  dazomet                                           benzofluor     chlorsulfuron DCPA                                              benzoylprop    chloroluron   desmediphan                                       bifenox        cimmethylin   desmetryn                                         ______________________________________                                    

EXAMPLE 1 3-(N,N-dimethylaminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5-methyl pyridine

To a stirred solution of 2.5 g (0.011 mole) of 2-(5-isopropyl-5-methyl-4-oxo-2-imidazolin-2 -yl)-5-methyl pyridine in 100 ml of dry tetrahydrofuran cooled to -70° C. under the presence of nitrogen was added dropwise a 9.68 ml of 2.5 molar n-butyllithium, thereby temperature was maintained below -65° C. The solution was stirred at -70° C. for 3 hours and a solution 1.96 g of N,N-dimethyl oxamic acid methyl ester(0.015 mole) in 10 ml of anhydrous tetrahydrofuran was added dropwise while maintaining the temperature below -65° C. After stirring another hour at -70° C., the solution was poured into water and extracted with methylene chloride. The combined organic phases were dried over magnesium sulfate, and evaporated under reduced pressure. Trituration of the residue with diethyl ether affored a crude solid which was recrystallized from a mixture of diethyl ether and methylene chloride to yield 1.67 g of a white solid (m.p=180°-182° C.).

EXAMPLE 2 Preparation of 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5-methyl-3 -(N-methyl-N-phenyl amino oxo acetyl)pyridine

To a stirred solution of 2.5 g(0.011 mole) of 2-(5-isopropyl-5-methyl-4-oxo-2-imidazolin-2 -yl)-5-methyl pyridine in 100ml of anhydrous tetrahydrofuran cooled to -70° C. under the presence of nitrogen was added dropwise a 9.68 ml of 2.5 molar n-butyllithium, thus maintaining temperature below -65° C. The solution was stirred at -70° C. for 3 hr and a solution 1.96 g of N-methyl-N-phenyl oxamic acid methyl ester(3.4 g, 0.016 mole) in 10 ml of anhydrous tetrahydrofuran was added dropwise while maintaining temperature below -65° C. After stirring another hour at -70° C., the solution was poured into water and extracted with methylene chloride. The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to give crude product. The crude product was purified by column chromatography to produce 1.76 g of pale yellow solid(m.p.=153°˜156° C.).

EXAMPLE 3 Preparation of 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5-methyl-3 -(N-methyl-N-phenyl amino oxo acetyl)pyridine

To a stirred solution containing 3.0g(0.13 mole)-2-(5-isopropyl-5-methyl-4-oxo-2-imidazolin-2 -yl)-5-methyl pyridine in 100ml dry THF at -70° C. under nitrogen was added dropwise 12.48 ml of 2.5 molar n-butyllithium in hexane without allowing the temperature to rise above -65° C. The solution was stirred at -70° C. for 3 hours and a solution 2.58 g of 3-methyloxazolin-2,4,5-trione(0.02 mole)in 10 ml dry THF was added dropwise while maintaining the temperature below -65° C. After stirring another hour at -70° C., the reaction mixture was allowed to attain room temperature. Reaction mixture was poured into water, the pH was adjusted to 7 with 5N H₂ SO₄ and extracted with methylene chloride.

The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to give crude product. The crude product was purified by column chromatography to afford 1.27 g of pale yellow solid(m.p.=174°-178° C.).

The Synthesis of using following compounds based upon said Examples 1˜3 was conducted : A-1˜A-39 compound as shown in the following general formular (I-A), B-1˜B-81 compound as shown in the following general formula (I-B), C-1˜C-34 compound as shown in the following general formula(I-C), and D-1˜D-6 compound as shown in the following general formular(I-D).

The herbicidal activity of said compound was measured in the greenhouse test.

                  TABLE 1                                                          ______________________________________                                          ##STR13##                                                                     ______________________________________                                          No.Compd.                                                                             K No.                                                                                   ##STR14##         m.p. (°C.)                           ______________________________________                                         A-1                                                                                             ##STR15##        124-127                                      A-2                                                                                             ##STR16##        156-159                                      A-3                                                                                             ##STR17##        145-148                                      A-4                                                                                             ##STR18##        179-181                                      A-5                                                                                             ##STR19##        216-219                                      A-6                                                                                             ##STR20##        188-184                                      A-7                                                                                             ##STR21##        150-152                                      A-8                                                                                             ##STR22##        136-139                                      A-9                                                                                             ##STR23##        156-159                                      A-10                                                                                            ##STR24##        189-193                                      A-11                                                                                            ##STR25##        150-153                                      A-12                                                                                            ##STR26##        127-129                                      A-13                                                                                            ##STR27##        196-198                                      A-14                                                                                            ##STR28##        174- 176                                     A-15                                                                                            ##STR29##        Amorphus Solid                               A-16                                                                                            ##STR30##        150-152                                      A-17                                                                                            ##STR31##        156-158                                      A-18                                                                                            ##STR32##        162-164                                      A-19                                                                                            ##STR33##        192-194                                      ______________________________________                                         Compd.                                                                         No.    K No.    R.sup.3 NR.sup.4  m.p. (°C.)                            ______________________________________                                         A-20                                                                                            ##STR34##        207-209                                      A-21                                                                                            ##STR35##         95-97                                       A-22                                                                                            ##STR36##        135-137                                      A-23                                                                                            ##STR37##        152-154                                      A-24                                                                                            ##STR38##        206-208                                      A-25                                                                                            ##STR39##        145-147                                      A-26                                                                                            ##STR40##        169-170                                      A-27                                                                                            ##STR41##        198-199                                      A-28                                                                                            ##STR42##        171-173                                      A-29                                                                                            ##STR43##        199-201                                      A-30                                                                                            ##STR44##        170-172                                      A-31                                                                                            ##STR45##        160-162                                      A-32                                                                                            ##STR46##        162-164                                      A-33                                                                                            ##STR47##        192-194                                      A-34                                                                                            ##STR48##        163-165                                      A-35                                                                                            ##STR49##        200-202                                      A-36                                                                                            ##STR50##        Amorphus Solid                               A-37            NHCH.sub.2 CH.sub.2 Cl                                                                           Amorphus                                                                       Solid                                        A-38            MeNCH.sub.2 CH.sub.2 OH                                                                          155-159                                      A-39                                                                                            ##STR51##        159- 163                                     ______________________________________                                    

                  TABLE 2                                                          ______________________________________                                          ##STR52##                                                                     Compd.                              m.p.                                       No.    K No.   R.sup.3 NR.sup.4     (°C.)                               ______________________________________                                         B-1            NH.sub.2                                                        B-2            MeNMe                185-187                                    B-3            EtNEt                156-158                                    B-4            n-PrN n-Pr           102-104                                    B-5            iso-PrN-iso-Pr       210-212                                    B-6                                                                                            ##STR53##           207-208                                    B-7                                                                                            ##STR54##           188-189                                    B-8                                                                                            ##STR55##           206-207                                    B-9                                                                                            ##STR56##           187-189                                    B-10                                                                                           ##STR57##           164-166                                    B-11                                                                                           ##STR58##           183-185                                    B-12                                                                                           ##STR59##           175-177                                    B-13                                                                                           ##STR60##           227-229                                    B-14                                                                                           ##STR61##           135-137                                    B-15                                                                                           ##STR62##           217-219                                    B-16                                                                                           ##STR63##           184-187                                    B-17                                                                                           ##STR64##           153-156                                    B-18                                                                                           ##STR65##           172-174                                    B-19                                                                                           ##STR66##           167-169                                    B-20                                                                                           ##STR67##           144-146                                    B-21                                                                                           ##STR68##           179-181                                    B-22                                                                                           ##STR69##           190-191                                    B-23                                                                                           ##STR70##           163-165                                    B-24                                                                                           ##STR71##           145-147                                    B-25                                                                                           ##STR72##            83-90                                     B-26                                                                                           ##STR73##           182-184                                    B-27                                                                                           ##STR74##           192-193                                    B-28                                                                                           ##STR75##           159-160                                    B-29                                                                                           ##STR76##           181-183                                    B-30                                                                                           ##STR77##           183-184                                    B-31                                                                                           ##STR78##           179-181                                    B-32                                                                                           ##STR79##           191-192                                    B-33                                                                                           ##STR80##           155-157                                    B-34                                                                                           ##STR81##           134-138                                    B-35                                                                                           ##STR82##           142-144                                    B-36                                                                                           ##STR83##           Amor- phus Solid                           B-37                                                                                           ##STR84##           188-189                                    B-38                                                                                           ##STR85##           154-157                                    B-39                                                                                           ##STR86##           134-136                                    B-40                                                                                           ##STR87##           171-172                                    B-41                                                                                           ##STR88##           181-183                                    B-42                                                                                           ##STR89##           145-149                                    B-43                                                                                           ##STR90##           165-167                                    B-44                                                                                           ##STR91##           162-163                                    B-45                                                                                           ##STR92##           187-189                                    B-46                                                                                           ##STR93##           180-182                                    B-47                                                                                           ##STR94##           200-201                                    B-48                                                                                           ##STR95##           212-215                                    B-49                                                                                           ##STR96##           182-184                                    B-50                                                                                           ##STR97##           167-169                                    B-51                                                                                           ##STR98##           168-170                                    B-52                                                                                           ##STR99##           155-157                                    B-53                                                                                           ##STR100##          155-157                                    B-54                                                                                           ##STR101##          169-171                                    B-55                                                                                           ##STR102##          169-171                                    B-56                                                                                           ##STR103##          158-160                                    B-57                                                                                           ##STR104##          175-177                                    B-58                                                                                           ##STR105##          174-176                                    B-59                                                                                           ##STR106##          173-175                                    B-60                                                                                           ##STR107##          178-180                                    B-61                                                                                           ##STR108##          167-169                                    B-62                                                                                           ##STR109##          170-171                                    B-63                                                                                           ##STR110##          159-162                                    B-64                                                                                           ##STR111##          172-175                                    B-65                                                                                           ##STR112##          164-167                                    B-66                                                                                           ##STR113##          187-189                                    B-67                                                                                           ##STR114##          187-189                                    B-68           NHCH.sub.3           174-178                                    B-69           NH-n-Pr              Amor-                                                                          phus                                                                           Solid                                      B-70           NH-t-Bu              Amor-                                                                          phus                                                                           Solid                                      B-71                                                                                           ##STR115##          189-191                                    B-72                                                                                           ##STR116##          142-144                                    B-73                                                                                           ##STR117##          143-145                                    B-74                                                                                           ##STR118##          167-168                                    B-75                                                                                           ##STR119##          107-112                                    B-76                                                                                           ##STR120##          145-148                                    B-77                                                                                           ##STR121##          168-169                                    B-78                                                                                           ##STR122##          159-161                                    B-79                                                                                           ##STR123##          159-161                                    B-80                                                                                           ##STR124##                                                     B-81                                                                                           ##STR125##                                                     ______________________________________                                    

                  TABLE 3                                                          ______________________________________                                          ##STR126##                                                                    Compd.                                                                         No.    K No.    R.sup.3 NR.sup.4  m.p. (°C.)                            ______________________________________                                         C-1             MeNMe             148-150                                      C-2             EtNEt             135-138                                      C-3             NPrNPr            114-116                                      C-4                                                                                             ##STR127##       149-150                                      C-5                                                                                             ##STR128##       169-171                                      C-6                                                                                             ##STR129##       161-165                                      C-7                                                                                             ##STR130##       154-156                                      C-8                                                                                             ##STR131##       Amorphus Solid                               C-9                                                                                             ##STR132##       216-218                                      C-10                                                                                            ##STR133##       139-141                                      C-11                                                                                            ##STR134##       185-187                                      C-12            MeNPh             131-134                                      C-13                                                                                            ##STR135##       179-181                                      C-14                                                                                            ##STR136##       134-136                                      C-15                                                                                            ##STR137##       149-151                                      C-16                                                                                            ##STR138##       Amorphus Solid                               C-17                                                                                            ##STR139##       118-120                                      C-18                                                                                            ##STR140##       152-154                                      C-19                                                                                            ##STR141##       Amorphus Solid                               C-20                                                                                            ##STR142##       155-157                                      C-21                                                                                            ##STR143##       163-165                                      C-22                                                                                            ##STR144##       136-138                                      C-23                                                                                            ##STR145##       177-179                                      C-24                                                                                            ##STR146##       140-142                                      C-25                                                                                            ##STR147##       133-135                                      C-26                                                                                            ##STR148##       155-158                                      C-27                                                                                            ##STR149##       152-154                                      C-28                                                                                            ##STR150##       131-133                                      C-29                                                                                            ##STR151##       181-183                                      C-30                                                                                            ##STR152##        88-90                                       C-31                                                                                            ##STR153##       181-184                                      C-32            NHEt              177-178                                      C-33                                                                                            ##STR154##        53-56                                       C-34            NH.sub. 2         197-203                                      ______________________________________                                    

                  TABLE 4                                                          ______________________________________                                          ##STR155##                                                                    Compd.                                                                         No.    K No.    R.sup.3 NR.sup.4  m.p. (°C.)                            ______________________________________                                         D-1             MeNMe             178-180                                      D-2                                                                                             ##STR156##       150-154                                      D-3                                                                                             ##STR157##       177-179                                      D-4                                                                                             ##STR158##       189-191                                      D-5                                                                                             ##STR159##       169-171                                      D-6                                                                                             ##STR160##       163-166                                      ______________________________________                                    

EXAMPLE 4 Post-emergence herbicidal evaluation of test compounds

The post-emergence herbicidal activity of the compounds of the invention is demonstrated by the following tests, wherein a variety of monocotyledonous and dicotyledonous plants are treated with test compounds dispersed in aqueous acetone mixtures. In the tests, seedling plants are grown in jiffy flats for two weeks. The test compounds are dispersed in 50/50 acetone/water mixtures containing 0.5% TWEEN(TM) 20, a polyoxyethylene sorbitan monolaurate surfactant, in sufficient quantity to provide the equivalent of about 0.06 kg of 10 kg per hectare of active compound when applied to the plants through a spray nozzle operating at 40 psi for a predetermined time. After spraying, the plants are placed on greenhouse benches and are cared for in the usual manner, commensurate with conventional greenhouse practices.

From 2 to 4 weeks after treatment, the seedling plants, are examined and rated according to the rating system provied below.

The data obtained are recorded in table 6 below.

    ______________________________________                                         [Rating System]                                                                Rating System    % Difference in Growth                                        ______________________________________                                         No effect         0                                                            Possible effect   1˜10                                                   Slight effect     1˜25                                                   Moderate effect  26˜40                                                   Definite injury  41˜60                                                   Herbicidal effect                                                                               61˜75                                                   Good herbicidal effect                                                                          76˜90                                                   Approaching complete kill                                                                       91˜99                                                   Complete kill    100                                                           ______________________________________                                    

In most cases the data are a single test, but in several instances, they are average values obtained from more than one test.

                  TABLE 5                                                          ______________________________________                                         Test to evaluate herbicidal activity                                           Abbr.   Scientific Name     Plants applied                                     ______________________________________                                         (Testgroup I: UPLAND SPECIES)                                                  LYPES   Lycopersicon esculentum MILL.                                                                      Tomato                                             TRZAW   Triticum aestivum L.                                                                               Wheat                                              GLXMX   Glycine max(L.) MERR.                                                                              Soybean                                            ZEAMX   Zea mays L.         Corn                                               DACGL   Dactylis glomerata L.                                                                              Orchardgrass                                       AMAVI   Amaranthus viridis L.                                                                              Pigweed                                            DIGSA   Digitaria sanguinalis(L.)                                                                          Large                                                      SCOP.               crabgrass                                          RUMJA   Rumex japonicus HOUTT.                                                                             Dock                                               AESIN   Aeschynomene indica L.                                                                             Indian                                                                         jointvetch                                         CAGHE   Calystegia japonica CHOISY                                                                         Bindweed                                           POLHY   Polygonum hydropiper L.                                                                            Smartweed                                          (Test group II: PADDY SPECIES)                                                 ORYSA   Oryza sativa L.     Rice                                               ECHOR   Echinochloa crus-galli P.                                                                          Barnyardgrass                                              Beauv. var. oryzicola OHWI                                             CYPDI   Cyperus difformis L.                                                                               Umbrellaplant                                      ANEKE   Aneilema keisak HASSK                                                                              Dayflower                                          ______________________________________                                    

EXAMPLE 5 Pre-emergence herbicidal evaluation of test compounds

The pre-emergence herbicidal activity of the compounds of the invention is examplified by the following tests in which the seeds of a variety of monocotyledonos and dicotyledonous plants are seperated mixed with potting soil in separated pint cups. After planting, the cups are sprayed with the selected aqueous acetone solution containing test compound in sufficient quantity to provide the equivalent of about 0.06 to 10 kg per hectare of test compound per cup. The treated cups are then placed on greenhouse benches, watered and cared for in accordance with conventional greenhouse procedures. From 2 to 4 weeks after treatment, the tests are terminated and each cup is examined and rated according to the rating system set forth above. The herbicidal proficiency of the active ingredients of the present invention is evident from the test results which are recorded in Table 6 below.

Table 6 below is represented pre-and post-emerergence herbicidal evaluation [PRIMARY SCREENING (Herbicide)]of test compounds.

    TABLE 6       PRIMARY SCREENING (Herbicide) KSC CHEM.   UPLAND WEED SPECIES PADDY      WEED SPECIES NO. REF. TYPE kg/ha LYPES TRZAW GLXMX ZEAMX DACGL AMAVI      DIGSA RUMJA POLHY AESIN CAGHE URYSA ECHOR CYPDI ANEXE         (A-1) PRE .25 100 100 90 90 70 100 100 80 100 100 100 60 70 70 70      .125 100 100 70 50 70 100 90 70 90 90 100 60 20 60 10    .06 100 90 40      10 35 100 90 10 90 70 90 0 0 50 10    .03 90 50 0 0 10 60 60 0 70 0 80 0      0 0 0    .015 90 10 0 0 0 0 20 0 0 0 10 0 0 0 0   POST .5 100 100 95 100      100 100 100 90 90 80 100 90 90 100 55    .25 100 100 90 90 80 100 100 80      80 70 100 90 80 100 50    .125 100 100 65 65 65 70 80 60 80 35 90 70 55      100 20    .06 80 90 40 0 55 70 55 40 80 35 50 15 20 40 20    .03 70 55      10 0 10 50 10 0 70 10 40 15 15 0 0  (A-2) PRE .25 80 60 10 70 70 80 90      20 70 50 80 60 35 90 25   POST .25 100 90 70 100 70 100 100 60 95 70 100      70 80 60 30  (A-3) PRE .25 100 90 60 60 65 90 100 40 90 50 65 70 20 90      70   POST .25 100 85 30 65 70 80 80 65 70 75 80 90 70 50 70  (A-4) PRE      .25 90 70 15 60 65 90 80 20 80 70 90 70 70 60 40   POST .25 100 90 85      100 80 100 100 70 90 90 100 90 90 80 70  (A-5) PRE .25 90 80 10 40 70 90      100 40 80 70 90 100 70 90 45   POST .25 100 100 100 100 100 100 100 95      100 95 100 90 90 70 100  (A-6) PRE .25 100 90 70 80 70 90 100 70 85 70      95 100 90 90 70   POST .25 100 100 90 100 100 100 100 70 100 90 100 90      100 100 90  (A-7) PRE .25 100 100 35 20 70 90 90 80  60 70 65 10 50 15      POST .25 100 100 80 100 70 100 70 50 90 60 100 90 55 40 10  (A-8) PRE      .25 70 30 0 20 60 80 60 50 70 0 0 55 20 60 50   POST .25 40 10 0 80 60      80 70 55 75 25 40 70 40 30 25  (A-9) PRE .25 100 100 70 100 100 100 100      90 95 100 100 20 20 80 40                  BE   POST .25 100 100 80 100      70 100 70 85 90 90 100 100 100 65 90  (A-10) PRE .25 100 100 90 100 90      100 100 85 90 90 100 100 40 70 0   POST .25 100 100 90 100 100 100 100      100  100 100 100 100 100 100  (A-11) PRE .25 90 70 30 20 80 70 90 10 90      35 50 15 0 70 0   POST .25 100 100 65 30 25 100 30 10 50 10 70 90 65 0      65  (A-12) PRE .25 100 95 90 100 90 100 100 90 95 90 100 85 100 100 90      POST .25 100 100 85 100 100 100 100 90 100 90 100 100 90 95 90  (A-13)      PRE .25 100 70 25 20 85 100 70 60 95 50 70 15 10 70 0   POST .25 90 65      40 0 0 100 25 10 70 10 70 65 15 0 0  (A-14) PRE .25 100 90 85 90 80 100      100 90 100 70 90 60 70 90 90   POST .25 100 80 80 80 75 90 80 70 90 75      95 95 100 75 95  (A-15) PRE .25 90 70 20 0 30 70 65 10  0 30 55 10 65 0       POST .25 100 100 75 100 100 100 35 10 70 60 100 80 65 65 25  (A-16) PRE      .25 80 70 30 0 20 70 60 10  15 30 60 0 65 30   POST .25 90 100 65 70 65      100 70 10 70 65 100 90 60 55 60  (A-17) PRE .25 80 35 10 0 10 60 60 15      0 50 10 20 0 0   POST .25 90 70 55 0 100 100 35 10 70 40 85 70 70 20 0      (A-18) PRE .25 100 90 80 100 80 100 100 90 100 80 90 50 25 90 30   POST      .25 100 90 70 90 65 100 80 55 90 85 100 90 100 100 90  (A-19) PRE .25 85      35 15 10 20 80 20 10 60 0 40 0 10 0 15   POST .25 90 20 10 0 10 10 0 0      50 0 60 65 55 0 20  (A-20) PRE .25 100 100 80 90 100 100 100 100 100 90      100 80 50 90 70   POST .25 100 100 70 40 100 100 100 85  90 100 100 100      100 60  (A-21) PRE .25 90 70 65 55 60 90 100 90  50 90 30 10 20 10      POST .25 100 100 80 70 70 100 60 60 90 80 100 100 60 70 70  (A-22) PRE      .25 100 90 60 80 100 90 100 80  70 80 100 0 80 80    .125 80 60 40 60 80      90 100 80   70 100 0 70 60    .06 80 50 30 50 80 80 100 80   65 100 0 70      30    .03 70 40 30 30 70 80 100 80   40 100 0 70 0   POST .25 100 90 70      65 65 100 100 50  75 80 90 100 70 90    .125 95 55 50 10 20 100 50 30      60 65 80 70 65 75    .06 50 10 20 0 20 80 10 20  10 50 80 30 60 50      .03 50 0 0 0 10 60 0 10  0 50 65 0 40 20  (A-23) PRE .25 100 100 75 90      90 90 100 60  100 100 35 20 65 65   POST .25 100 100 80 65 70 100 100 20       90 100 70 90 100 60  (A-24) PRE .25 100 100 85 90 100 90 100 80  95 90      70 15 65 70   POST .25 100 100 90 70 100 100 100 15  80 100 90 100 90 60       (A-25) PRE .25 85 35 0 10 70 80 100 60  0 80   POST .25 90 15 0 10 30      90 90 35  0 90 65 60 100 20  (A-26) PRE .25 90 55 15 10 55 100 60 40 85      20 70 20 10 20 10   POST .25 90 60 20 0 40 70 15 20 75 30 60 70 30 0 15      (A-27) PRE .25 100 95 80 100 90 100 100 95 95 95 95 70 50 80 75   POST      .25 100 100 100 100 65 100 80 70 9090 100 70 100 40 90  (A-28) PRE .25      100 90 85 90 80 100 100 80 90 90 100 60 30 70 40   POST .25 100 90 80 90      75 100 75 70 100 90 100 90 90 60 100  (A-29) PRE .25 100 100 80 90 90      100 100 90  90 100 100 40 80 0    .125 90 70 40 50 80 100 100 80  50 80      100 0 70 0    .06 80 60 20 20 70 80 70 80  10 50 100 0 60 0    .03 70 40      10 0 65 70 30 70  0 20 100 0 60 0   POST .25 100 95 70 65 100 100 100      100  90 100 90 95 100 90    .125 90 90 65 10 60 100 95 30  70 80 85 75      80 85    .06 100 70 45 0 10 100 40 10  0 55 80 40 50 70    .03 70 20 0 0      0 80 0 0  0 30 70 20 50 10  (A-30) PRE .25 70 40 10 0 0 65 0 0 30 0 20      10 0 0 0   POST .25 100 90 70 30 70 100 65 30  85 100 60 60 70 90      (A-31) PRE .25 100 100 80 90 90 100 100 70 100 100 100 80 35 80 70      POST .25 100 100 90 55 90 100 70 30  90 100 90 100 100 60  (A-32) PRE      .25 100 90 85 90 80 100 100 50  90 95   POST .25 100 100 90 100 90 100      100 70  100 100 65 100 100 90  (A-33) PRE .25 100 90 65 85 85 100 100 25      80 80 90 35 20 70 20   POST .25 100 100 80 100 100 100 70 70  90 100 90      100 100 100  (A-34) PRE .25 90 65 50 40 60 100 50 15 65 40 90 30 10 80 0        POST .25 100 70 60 10 40 100 25 25  60 70 60 60 60 80  (A-35) PRE .25      80 65 15 5 50 100 70 30  40 70 0 0 0 0   POST .25 100 100 80 15 60 100      60 40 90 50 80 80 50 30 50  (A-36) PRE .25 70 70 20 10 35 80 75 20  15      30 30 0 10 0   POST .25 90 100 50 10 25 100 30 10 70 20 70 100 30 10 10      (A-37) PRE .25 80 35 5 0 20 90 15 0 65 0 80 0 0 0 0   POST .25 90 60 50      0 20 100 15 10 75 20 90 10 20 0 0  (A-38) PRE .25 100 100 70 70 90 100      100 90 90 75 100 60 60 20 70   POST .25 100 100 70 65 80 100 65 80  70      100 100 100 100 90  (A-39) PRE .25 90 100 90 75 80 100 100 70  80 70      POST .25 70 60 40 10 20 100 30 10  10 70 10 0 0 20  (B-1) PRE .5 100 30      0 0 60 70 100 55 80 20 80 70 70 90 90    .25 80 0 0 0 40 60 70 30 80 0      80 40 50 70 10    .125 70 0 0 0 0 0 65 0 30 0 10 0 0 70 0    .06 70 0 0      0 0 0 10 0 10 0 0 0 0 60 0   POST .5 90 40 5 0 80 70 90 10 80 55 60 70      60 50 30    .25 80 5 0 0 60 50 65 0 50 10 40 50 60 20 10    .125 70 0 0      0 10 20 20 0 10 0 10 50 15 0 0    .06 40 0 0 0 0 10 0 0 0 0 0 20 0 0 0      (B-2) PRE .5 100 90 90 90 90 90 100 90 90 90 90 100 90 100 90    .25 100      90 65 70 70 90 100 90 90 90 90 100 90 100 80    .125 100 85 10 70 70 90      100 80 90 80 90 90 90 90 70    .06 90 70 0 30 60 90 100 80 90 65 90 80      80 90 60    .5 100 90 75 90 90 90 100 90 90 95 100 100 100 100 95    .25      100 90 65 85 90 90 100 90 90 70 100 100 100 90 90    .125 100 85 30 35      85 90 100 80 80 70 90 100 90 90 80    .06 95 65 10 0 70 80 100 80 80 35      90 60 60  50    .03 90 10 0 0 60 80 90 40 70 0 65  30 55 0   POST .5 100      90 85 80 90 90 100 70 90 100 100 90 100 100 50    .25 100 90 65 80 80 90      100 70 90 70 100 80 100 100 50    .125 100 80 40 65 70 80 100 60 90 60      100 70 90 100 40    .06 100 50 15 10 65 70 90 50 80 60 60 70 75 100 40      (B-3) PRE .25 90 60 10 55 70 90 100 70 90 30 90 90 80 90 60   POST .25      100 65 10 30 65 90 90 70 90 60 65 80 100 70 45  (B-4) PRE .25 90 50 10      20 70 90 100 55 90 10 80 100 70 90 70   POST .25 100 65 10 40 65 90 90      35 70 25 50 70 80 70 30  (B-5) PRE .25 80 10 0 15 60 90 90 40 80 0 80      100 90 90 80   POST .25 100 65 10 30 60 90 80 40 80 50 60 70 90 90 35      (B-6) PRE .25 100 80 40 30 90 90 100 70 90 50 100 90 80 90 60   POST .25      100 80 50 65 100 90 100 100 90 80 100 90 100 90 50  (B-7) PRE .25 100 80      25 30 90 90 100 70 90 50 90 100 95 90 60   POST .25 100 90 60 80 90 90      100 70 90 90 100 90 100 90 50  (B-8) PRE .25 100 90 40 65 90 90 100 60      90 60 100 100 95 90 90   POST .25 100 70 80 70 100 90 100 70 90 85 100      90 100 90 60  (B-9) PRE .25 100 90 0 70 80 90 100 70 80 65 100 100 100      90 85   POST .25 100 90 65 60 90 100 100 70 90 80 100 90 100 95 70      (B-10) PRE .25 90 40 10 30 90 100 100 90  40 70 100 60 90 60   POST .25      100 70 25 30 100 100 90 80 100 65 90 90 85 90 30  (B-11) PRE .25 100 80      50 30 70 90 100 80 90 50 90 90 20 90 60   POST .25 100 90 55 60 80 90      100 80 80 80 100 100 100 90 70  (B-12) PRE .25 100 65 10 10 100 95 100      90 90 70 80 90 90 90 10   POST .25 100 60 40 45 90 100 100 90 100 90 100      100 100 100 65  (B-13) PRE .25 100 70 65 75 70 80 95 40 80 60 95 90 70      90 50   POST .25 100 60 30 70 90 90 100 50 90 65 100 70 100 60 20      (B-14) PRE .25 100 90 60 60 80 90 100 90 90 90 100 100 90 100 25   POST      .25 100 90 50 80 90 100 100 90 90 90 100 100 100 80 80  (B-15) PRE .25      100 90 35 90 100 100 100 95  75 90 100 100 95 70   POST .25 100 75 60 90      100 100 100 90 100 80 100 100 100 100 50  (B-16) PRE .25 90 30 10 10 90      90 100 70 90 10 70 100 85 95 35   POST .25 100 30 30 10 70 100 70 60 80      40 90 100 100 80 40  (B-17) PRE .5 100 90 70 100 95 90 100 90 90 90 100      100 100 100 80    .25 100 90 50 65 90 90 100 90 90 80 100 100 100 90 90        .125 100 70 10 20 80 90 100 90 90 70 100 85 70 90 80    .06 90 30 0 0      70 85 90 80 80 35 90 50 65 70 35    .03 90 15 0 0 60 70 80 70 70 10 60      30 20 10 10   POST .5 100 100 90 90 100 100 100 90 100 100 100 90 100      100 65    .25 100 70 15 5 100 100 100 80 85 85 100 90 90 100 65    .125      90 35 10 0 60 100 100 65 70 55 100 70 80 100 55    .06 70 10 0 0 25 30      60 10 50 10 90 10 25 70 20    .03 65 10 0 0 0 20 50 0 40 0 55 0 0 20 0      (B-18) PRE .25 80 50 15 0 70 90 100 85  0 65 60 30 90 10   POST .25 90      10 10 0 70 0 100 80 100 25 70 70 70 70 15  (B-19) PRE .25 100 60 10 25      90 95 100 90  30 90 70 60 90 20   POST .25 100 60 20 50 100 100 100 90      100 90 100 100 90 90 40  (B-20) PRE .25 80 0 0 0 65 90 95 50  0 70 70 70      90 10   POST .25 100 65 20 20 100 100 100 90 100 70 100 70 80 90 60      (B-21) PRE .25 80 0 0 0 60 70 90 30  0 65 50 0 70 20   POST .25 100 15      20 0 50 90 100 20 90 25 100 70 70 70 0  (B-22) PRE .25 100 80 65 65 90      100 100 100  90 100 100 80 90 70    .125 100 70 30 30 90 100 100 100  75      100 70 20 90 60    .06 90 40 10 0 80 100 100 70  55 80 60  50 20    .03      90 10 0 0 70 100 90 70  15 70 0 50 0 30    .015 70 0 0 0 35 85 70 20  0      70 0 0 0 0    .25 100 70 50 40 90 100 100 90  80 90 100 40 90 100    .12      90 60 20 20 90 100 100 80  70 80 100 20 90 80    .06 90 30 0 0 80 90 100      65  30 70 90 0 80 70    .03 80 10 0 0 70 90 100 50  0 60 80 0 80 10      POST .25 100 50 10 40 100 100 100 80  80  95 100 100 65    .12 100 50 0      0 90 100 95 60  65  90 80 90 20    .06  0 0 0 75 100 60 40  30  50 65 50      0    .03  0 0 0 30 95 10 20  20  20 20 50 0  (B-23) PRE .25 100 90 20 30      90 100 100 90 90 90 100    .125 90 55 5 0 90 100 100 80 90 60 100    .06      90 20 0 0 80 100 90 65 80 30 80    .03 80 10 0 0 60 90 70 10 65 10 80      (B-24) PRE .25 100 90 30 50 100 100 100 90 100 80 100 100 100 100 80      POST .25 100 65 30 20 95 100 100 70 100 75 100 95 100 100 70  (B-25) PRE      .25 80 10 0 0 60 100 70 65 80 0 40 65 55 90 0   POST .25 90 30 15 10 70      100 100 70  65 100 90 100 100 60  (B-26) PRE .1 100 35 10 35 85 90 100      65 95 75 80 100 90 90 70    .01 60  0 0 0 40 30 0 20 0 30 0 0 0 0   POST      .1 100 50 10 0 90 100 100 60 100 80 100 90 90 90 60    .01 40 10 0 0      100 80 10 70 20 60 10 15 10 0  (B-27) PRE .1 90 30 0 10 70 90 100 60 95      70 80 90 50 90 70   POST .1 100 20 10 0 100 100 100 70 100 70 100 90 90      100 70  (B-28) PRE .25 100 60 40 50 100 100 100 100  80 90 100 70 100 70         .125 80 40 20 10 90 100 100 80  70 80 100 20 100 30    .06 80 0 0 0      80 100 100 80  30 70 100 0 80 0    .03 70 0 0 0 70 80 90 70  10 50 100 0      80 0   POST .25 100 65 30 30 100 100 100 100  70 100 100 100 100 40      .125 85 30 0 0 90 100 60 50  50 100 60 60 80 20    .06 70 20 0 0 100 100      50 30  0 60 30 30 30 0    .03 60 0 0 0 30 85 0 0  0 60 20 20 0 0  (B-29)      PRE .25 100 85 30 80 100 100 100 90 90 85 100 90 85 100 30   POST .25      100 75 30 25 100 100 100 100  90 100 100 100 100 60  (B-30) PRE .25 100      90 30 40 100 100 100 90 100 80 90    .125 90 30 0 0 90 100 100 70 80 40      90    .06 90 15 0 0 60 60 40 60 70 0 25    .03 65 0 0 0 10 50 0 0 25 0      25  (B-31) PRE .25 100 70 40 50 100 100 100 90  90 90 100 90 100 90      .125 100 40 20 10 80 90 100 80  40 80 100 50 100 40    .06 100 30 0 0 80      80 90 80  20 70 100 20 80 0    .03 80 0 0 0 70 70 80 70  0 40 100 0 80 0        POST .25 100 65 40 55 100 100 100 85  80 100 100 80 100 50    .125 100      30 10 0 100 100 100 75  60 100 50 30 70 40    .06 100 0 0 0 90 100 65 40       30 65 55 20 70 50    .03 100 0 0 0 20 80 50 20  10 60 10 0 60 0  (B-32)      PRE .25 100 60 40 50 100 100 100 80  90 90 100 50 100 30    .125 90 40      30 10 80 90 100 70  40 70 100 40 100 0    .06 90 10 10 0 70 90 100 65      20 60 90 0 80 0    .03 80 0 0 0 70 80 80 60  0 10 80 0 70 0   POST .25      100 60 35 0 100 100 100 80  75 100 100 100 100 20    .125 90 20 10 0 80      100 90 40  50 90 60 50 85 20    .06 70 0 0 0 70 100 80   30 60 10 40 100      20    .03 50 0 0 0 20 85 0 30  0 40 0 0 50 0  (B-33) PRE .25 100 70 40      60 90 100 100 90  90 100 100 90 100 90    .125 90 40 10 20 90 90 100 90      50 80 100 50 100 30    .06 80 10 0 0 80 80 100 80  0 40 100 30 80 20      .03 70 0 0 0 70 80 80 70  0 30 100 0 80 0   POST .25 100 75 40 65 100      100 100 100  75 100 100 95 100 40    .125 85 30 10 0 100 90 100 65  55      100 80 60 100 30    .06 75 10 0 0 100 100 100 40  20 100 20 20 60 0      .03 55 0 0 0 20 80 20 10  0 50 0 0 60 0  (B-34) PRE .25 100 90 45 50 90      100 100 65 100 100 100 100 80 90 60   POST .25 100 90 75 60 100 100 100      100 100 100 100 100 100 100 35  (B-35) PRE .25 100 65 30 40 70 90 100 60      100 90 90 100 100 95 70   POST .25 100 60 65 60 100 100 100 100 100 100      100 90 100 100 60  (B-36) PRE .25 100 65 35 30 90 100 100 100  95 95 100      90 90 90   POST .25 100 70 30 25 100 100 100 90 100 90 100 100 100 100      60  (B-37) PRE .25 100 90 70 30 80 100 100 70 100 100 100 100 100 100 90        POST .25 100 80 50 55 100 100 100 90 100 90 100 100 100 100 70               BEI  (B-38) PRE .25 100 90 40 70 80 90 100 80 100 100 95 100 95      100 70   POST .25 100 65 10 10 90 100 100 100 90 80 100 100 100 100 65         BE I  (B-39) PRE .25 100 10 10 0 90 100 100 90 90 70 80 100 80 100 60        POST .25 90 10 0 0 80 100 80 70  0 100 90 100 100 20  (B-40) PRE .25      90 10 0 0 70 100 90 65 90 20 75 15 20 10 10   POST .25 90 0 0 0 60 20 60      30 75 20 70 70 65 0 15  (B-41) PRE .25 100 80 65 55 80 100 100 70 90 100      100 100 100 100 70   POST .25 100 70 35 10 100 100 100 90 100 85 100 100      100 100 60  (B-42) PRE .25 100 90 40 60 90 100 100 90 100 80 100 100 100      100 60   POST .25 100 50 35 25 100 100 100 90 100 70 100 90 100 90 70      (B-43) PRE .25 100 70  30 95 100 100 100  90 100 100 100 100 90   POST      .25 100 65 15 0 80 75 100 75  70 100 90 90 90 60  (B-44) PRE .25 100 65      40 50 90 100 100 80  70 90 100 50 100 60    .125 90 20 10 5 80 90 90 70      0 60 100 0 100 40    .06 80 10 0 0 70 70 60 70  0 30 100 0 100 10    .03      65 0 0 0 40 70 55 60  0 0 100 0 100 0                  BECA   POST .25      95 20 20 10 95 100 60 70  50 95 100 95 95 55       B A    .125 90 10 0 0      90 95 60 50  60 80 75 20 90 10    .06 75 0 0 0 50 90 65 30  40 50 50 0      60 0    .03 60 0 0 0 20 70 40 20  20 50 40 0 50 0  (B-45) PRE .25 100 60      45 30 100 100 100 100  90 90 100 100 90 70   POST .25 100 60 25 30 100      100 100 70  80 100 100 100 100 60  (B-46) PRE .25 100 85 55 90 100 100      100 90  90 100   POST .25 100 60 20 10 100 100 100 90  90 100 90 100 100      65  (B-47) PRE .25 90 60 15 15 90 90 100 75  80 90   POST .25 100 30 10      0 100 100 100 90  80 100 90 100 100 90  (B-48) PRE .25 90 70 10 0 90 95      100 70 100 70 90 90 100 100 70   POST .25 100 60 35 0 100 100 100 90 100      90 100 90 100 100 35  (B-49) PRE .25 80 0 0 0 60 100 100 70 75 10 70 100      90 90 50   POST .25 70 35 0 0 60 100 35 35  30 80 60 50 70 60  (B-50)      PRE .25 90 70 30 30 80 90 100 60 95 75 95 100 90 90 40   POST .25 100 60      15 0 100 100 100 80 95 90 100 80 70 100 30  (B-51) PRE .25 100 90 50 60      80 100 100 50 100 90 95 100 90 90 70   POST .25 100 65 30 20 100 100 100      90 100 90 100 100 100 100 60  (B-52) PRE .25 80 20 10 0 80 100 100 100      40 50 100 70 100 70    .125 80 10 0 0 70 80 70 50  0 40 100 0 80 30      .06 70 10 0 0 70 80 60 50  0 20 100 0 70 0    .03 60 0 0 0 65 65 30 40      0 10 100 0 70 0   POST .25 100 30 30 30 100 100 100 90  70 100 0 95 100      60    .125 20 20 0 0 10 20 0 0  0 0 0 0 0 0    .06 0 0 0 0 0 0 0 0  0 0      0 0 0 0    .03 0 0 0 0 0 0 0 0  0 0 0 0 0 0  (B-53) PRE .25 100 70 60 75      100 100 100 100  90 90   POST .25 100 40 30 0 100 100 100 90  65 100 90      100 100 80  (B-54) PRE .25 100 90 35 30 100 100 100 90 95 90 100    .125      100 60 5 20 90 100 100 90 90 65 90    .06 90 25 0 0 70 100 100 50 80 30      90    .03 90 10 0 0 65 100 75 30 70 10 60  (B-55) PRE .25 100 90 50 60      100 100 100 90 95 90 100    .125 100 60 0 0 90 100 100 80 90 70 100      .06 90 50 0 0 80 90 80 60 80 10 90    .03 80 10 0 0 60 10 30 5 65 0 60      (B-56) PRE .25 100 90 20 35 85 100 100 90 100 75 100 80 95 100 10   POST      .25 100 20 10 0 90 90 100 75 95 70 100 95 100 100 70  (B-57) PRE .25 90      35 15 20 80 90 100 70  70 90   POST .25 100 30 15 0 80 100 100 80  40      100 90 80 100 55  (B-58) PRE .25 100 60 25 70 80 90 100 65  70 90   POST      .25 100 30 35 0 100 100 100 90  90 100 70 100 100 90  (B-59) PRE .25 100      70 25 40 90 90 100 70 100 90 90 100 100 100 80    .06 90 0 0 0 70 60 90      40 90 40 70 60 40 50 30   POST .25 100 70 65 15 100 100 100 100 100 95      100 100 100 100 40    .06 80 20 0 0 70 100 70 45 90 15 90 10 40 10 10      (B-60) PRE .25 100 80 60 70 100 100 100 90 90 90 100 100 80 100 70      POST .25 100 75 30 0 100 100 100 80  70 100 100 100 100 90  (B-61) PRE      .25 100 50 30 20 100 100 100 80  70 80 100 80 100 70    .125 90 30 20 0      100 100 100 80  40 70 100 0 100 40    .06 90 20 10 0 100 100 100 80  0      60 100 0 80 20    .03 70 0 0 0 80 80 70 80  0 20 100 0 80 0   POST .25      100 30 20 10 85 100 95 60  75 100 100 95 100 65    .125 95 20 0 0 75 100      90 30  40 95 100 60 75 20    .06 60 10 0 0 30 90 50 0  0 60 70 45 60 0       .03 55 0 0 0 20 65 30 0  0 50 65 20 70 0  (B-62) PRE .25 100 70 50 60      100 100 100 80  80 80 100 60 100 60    .125 80 50 20 10 90 90 100 80  40      70 100 30 100 40    .06 80 20 0 0 90 90 100 70  0 60 100 30 100 0    .03      80 0 0 0 90 80 100 65  0 40 100 0 80 0   POST .25 100 40 20 10 100 100      100 65  70 100 100 100 100 50    .125 100 20 10 0 100 100 90 70  60 100      90 100 90 50    .06 80 10 0 0 30 100 60 70  20 75 75 65 80 30    .03 60      0 0 0 20 85 40 20  0 50 60 30 70 0  (B-63) PRE .25 100 65 15 10 70 100      100 70 80 40 90 100 60 90 15   POST .25 100 45 10 0 70 100 70 70  55 100      100 100 100 60  (B-64) PRE .25 100 85 50 65 90 100 100 70 100 100 100      100 100 100 80   POST .25 100 60 55 55 100 100 100 100 100 90 100 90 100      100 40  (B-65) PRE .25 100 90 60 65 90 90 100 70 100 90 100 100 100 100      30   POST .25 100 80 55 45 100 100 100 100 100 100 100 100 100 100 30      (B-66) PRE .25 100 70 30 40 90 100 100 65 100 90 90 100 100 100 80      POST .25 100 80 60 50 100 100 100 100 100 90 100 100 100 100 85  (B-67)      PRE .25 90 85 45 60 90 100 100 80 100 80 90 100 100 100 85    .06 85 20      10 0 55 90 100 20 100 60 70 70 65 70 30   POST .25 100 70 60 35 100 100      100 100 100 100 100 100 100 100 35    .06 90 30 0 0 90 100 90 90 90 40      100 60 70 100 10  (B-68) PRE .25 100 90 65 80 90 100 100 90 100 70 100      90 90 90 30    .25 100 85 30 35 70 100 100 90 90 90 100 100 100 90 50      .12 90 65 15 5 70 90 100 90 90 25 80 50 40 75 15        B    .06 90 25 0      0 60 90 90 80 90 20 80 10 0 0 0    .03 80 15 0 0 20 60 60 25 80 0 60 0 0      0 0    .015 65 0 0 0 0 0 10 0 15 0 35 0 0 0 0   POST .25 100 60 20 10 65      100 85 75 100 65 100 90 80 0 20    .125 90 15 10 0 60 100 75 55 100 30      100 70 60 0 10    .06 70 0 10 0 20 50 50 40 100 0 60 55 40 0 0    .03 60      0 0 0 0 20 0 0 70 0 50 15 0 0 0  (B-69) PRE .25 100 55 0 0 70 85 100 60      80 15 80 10 30 50 10   POST .25 100 50 20 0 80 90 100 80 100 60 100 100      80 60 30  (B-70) PRE .25 40 10 0 0 15 25 40 20  0 25 10 0 0 0   POST .25      80 10 10 0 10 80 70 60 80 0 65 80 60 40 10  (B-71) PRE .25 80 15 10 0 70      100 100 90 90 25 90 10 0 70 0   POST .25 90 0 25 0 65 100 70 70 90 25 90      70 65 0 0  (B-72) PRE .25 100 80 60 80 100 90 100 90  80 90   POST .25      100 10 15 0 90 100 100 70  70 100 90 80 100 60  (B-73) PRE .25 100 70 40      50 90 100 100 70  75 85   POST .25 100 60 50 15 90 100 100 80  70 100 90      90 100 90  (B-74) PRE .25 100 90 65 70 100 100 100 100 100 100 100 100      100 90 70   POST .25 100 85 55 15 100 100 100 90 100 90 100 100 100 100      60  (B-75) PRE .25 100 80 30 20 85 100 100 70 100 100 100 100 90 100 60       POST .25 100 65 10 0 100 100 100 80 100 85 100 95 100 100 65  (B-76)      PRE .25 100 90 70 70 90 100 100 70 100 100 100 100 100 100 90   POST .25      100 65 50 30 100 100 100 100 100 90 100 90 100 100 60  (B-77) PRE .25      100 90 30 60 100 100 100 100 100 90 100 100 100 100 70   POST .25 100 70      30 30 100 100 100 90 90 80 100 100 100 100 70  (B-78) PRE .25 90 70 20      30 80 100 100 40 100 100 100 100 100 95 70   POST .25 100 50 20 0 100      100 100 85 95 75 100 100 100 100 60  (B-79) PRE .25 100 80 60 90 100 100      100 80 100 90 100 100 80 100 65   POST .25 100 70 65 30 100 100 100 90      100 90 100 90 100 100 70  (C-1) PRE .5 90 85 0 10 35 90 90 20 90 10 90      90 90  90    .25 70 70 0 10 20 90 90 15 90 0 90 90 80  60    .125 70 25      0 0 20 90 90 0 90 0 60 80 70  50    .06 65 0 0 0 0 85 80 0 90 0 60 65 50       15                   I   POST .5 100 90 0 65 70 70 90 65 90 25 90 90 90      100 80    .25 90 60 0 0 60 70 90 50 90 10 90 90 90 100 70    .125 80 15      0 0 60 70 70 15 90 0 80 80 85 100 35    .06 60 0 0 0 35 55 70 0 70 0 40      65 70 90 10  (C-2) PRE .25 100 60 0 30 60 90 100 50 90 0 80 90 70 90 50       POST .25 70 10 0 0 60 90 65 10 70 10 30 60 55 50 15  (C-3) PRE .25 90      20 0 0 55 90 90 10 80 0 60 100 70 80 50   POST .25 80 10 0 0 30 80 65 10      60 0 35 70 60 40 10  (C-4) PRE .25 100 70 0 20 70 90 100 60 90 0 100 90      90 80 70   POST .25 100 15 0 15 70 90 90 40 80 0 95 80 70 80 25  (C-5)      PRE .25 100 70 0 15 90 100 100 70 90 0 100 100 90 90 60   POST .25 100      60 0 10 60 90 80 35 70 0 80 70 100 90 60  (C-6) PRE .25 100 60 0 10 50      80 100 20 80 10 95 100 100 90 70   POST .25 100 60 0 10 50 100 90 25 90      0 100 70 100 100 20  (C-7) POST .25 70 10 0 0 40 100 70 15 70 0 65 80 70      60 0  (C-8) PRE .25 100 40 0 0 65 95 100 90 90 0 70 100 30 90 0   POST      .25 95 15 20 0 20 100 65 10 75 0 100 100 100 50 35  (C-9) PRE .25 80 60      0 0 40 80 95 15 80 0 85 90 60 90 15   POST .25 90 35 10 0 20 90 100 0 70      0 100 70 80 20 0  (C-10) PRE .25 100 40 0 15 65 90 100 80  0 80 100 80      90 20   POST .25 100 40 10 10 65 100 90 40 90 0 100 100 100 100 30      (C-11) PRE .25 100 70 0 25 70 90 100 85  0 70 100 100 90 50   POST .25      100 70 0 30 60 100 100 70 90 0 100 100 90 100 20  (C-12) PRE .25 90 75 0      10 70 90 100 60 90 0 100 100 95 90 70        B   POST .25 100 70 0 10 65      100 85 20 80 0 90 70 100 80 60  (C-13) PRE .25 90 20 0 0 60 90 85 35 70      10 60 75 70 90 0   POST .25 80 15 10 0 20 100 70 10 60 0 60 30 65 0 0      (C-14) PRE .25 100 60 0 20 85 90 100 90  0 95 100 95 100 25   POST .25      70 60 10 10 50 100 80 50 80 0 100 90 70 65 30  (C-15) PRE .25 10 0 0 0 0      55 0 0 20 0 0 30 0 50 0   POST .25 60 15 10 0 20 65 20 20  0 50 60 50 20      0  (C-16) PRE .25 20 0 0 0 0 100 50 10  15 10 10 10 50 0   POST .25 30 0      0 0 0 50 40 0 40 0 50 30 20 60 0  (C-17) PRE .25 90 60 0 15 90 90 100 90      95 0 95 60 90 90 25   POST .25 100 25 0 0 50 100 95 45 75 0 80 70 100 70      20  (C-18) PRE .25 100 40 10 20 90 100 100 80  0 80 100 60 90 60    .125      80 20 0 0 90 80 100 70  0 70 100 20 70 50    .06 70 0 0 0 80 80 100 65      0 60 100 0 70 30    .03 70 0 0 0 80 70 70 60  0 50 100 0 70 0   POST .25      100 10 0 0 30 100 60 30  0 100 100 100 100 50    .125 80 0 0 0 20 100 50      20  0 75 90 65 80 20    .06 50 0 0 0 20 75 10 10  0 60 65 30 65 0    .03      30 0 0 0 0 65 0 10  0 20 60 30 60 0          AB  B  (C-19) PRE .25 90 20      0 10 80 90 100 70  15 80 100 90 90 70   POST .25 90 10 0 0 65 100 90 20      0 100 90 90 100 40  (C-20) PRE .25 80 0 0 0 15 50 25 0 60 0 0 0 10 50 0       POST .25 75 15 10 0 0 50 20 0 20 0 45 25 55 0 0  (C-21) PRE .25 95 60 0      15 80 90 100 80 90 0 90 100 90 90 60   POST .25 80 20 0 0 70 85 90 60  0      80 90 100 90 60  (C-22) PRE .25 100 50 5 5 100 90 100 80  0 90 100 65      100 70    .125 80 30 0 0 100 90 100 70  0 70 100 40 100 40    .06 80 10      0 0 90 80 100 60  0 40 100 20 90 0    .03 70 0 0 0 80 80 65 60  0 10 90      0 90 0   POST .25 100 30 10 10 50 100 100 40  0 95 100 95 95 50    .125      75 20 0 0 30 100 80 20  0 70 95 60 70 0    .06 65 10 0 0 20 95 50 10  0      50 65 30 70 0    .03 55 0 0 0 10 90 0 10  0 45 50 0 50 0  (C-23) PRE .25      90 40 0 10 70 90 95 70  0 90   POST .25 100 20 10 10 50 90 90 50  0 90      65 50 80 70  (C-24) PRE .25 90 60 0 10 70 100 100 70  15 80   POST .25      90 10 0 0 40 70 70 20  0 100 70 70 90 65  (C-25) PRE .25 90 40 0 35 70      90 100 70  10 90   POST .25 100 30 15 10 65 100 100 65  0 100 100 100 90      85  (C-26) PRE .25 85 35 0 10 70 80 100 60  0 80   POST .25 90 15 0 10      30 90 90 35  0 90 65 60 100 20  (C-27) PRE .25 80 30 0 0 60 70 90 55  0      85   POST .25 100 10 0 0 40 100 90 20  0 90 90 100 100 30  (C-28) PRE      .25 90 30 5 5 90 100 100 90  0 60 100 20 100 40    .125 80 20 0 0 70 80      80 80  0 40 100 0 80 0    .06 70 10 0 0 60 70 70 70  0 30 90 0 70 0      .03 60 0 0 0 50 70 40 65  0 0 80 0 70 0   POST .25 95 30 10 0 30 100 65      20  0 60 95 90 95 20    .125 65 10 0 0 20 100 20 0  0 50 80 40 65 0      .06 40 0 0 0 0 60 0 0  0 10 60 0 90 0    .03 40 0 0 0 0 50 0 0  0 10 55      0 90 0  (C-29) PRE .25 70 10 0 0 30 60 70 0  0 40   POST .25 90 30 25 0      10 70 65 15  0 100 65 65 70 15  (C-30) PRE .25 80 25 0 0 25 90 85 20  0      70   POST .25 70 0 0 0 30 60 65 0  0 70 55 25 60 0  (C-31) PRE .25 70 0      0 0 50 90 85 10 70 0 60 80 10 70 0   POST .25 70 10 0 0 30 70 60 30  0      55 70 50 20 10  (C-32) PRE .25 90 40 0 10 100 100 100 70  30 85   POST      .25 80 15 0 0 50 70 100 50  0 90 60 70 90 30  (C-33) PRE .25 80 15 0 0      100 100 90 50  0 60   POST .25 70 10 20 0 0 40 20 0  0 45 50 0 0 0      (D-1) PRE .25 90 90 0 70 80 90 100 90 90 20 90 90 90 100 90   POST .25      40 60 0 70 60 70 80 55 80 25 40 70 60 70 15  (D-2) PRE .25 90 90 0 70 70      90 90 80 90 15 70 100 60 100 70   POST .25 40 60 0 70 75 70 60 70 80 10      65 70 65 70 10  (D-3) PRE .25 90 90 0 80 70 90 90 90 90 0 90 90 70 90 70        POST .25 55 30 0 65 70 70 60 60 70 10 65 90 85 70 55  (D-4) PRE .25 90      90 65 60 70 90 70 50 80 50 65 60 30 50 50   POST .25 100 90 90 100 80 80      90 80 80 80 100 100 100 50 90  (D-5) PRE .25 90 90 0 70 60 90 90 80 90 0      90 90 70 90 70   POST .25 60 35 0 65 60 70 70 55 70 15 45 70 35 65      30

EXAMPLE 6 Wettable Powder

3-N-methyl-N-3-fluorophenylaminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2 -yl)-5methylpyridine : 50%

sodium alkylnaphthalenesulfonate: 2%

low viscosity methyl ceollulose : 2%

diatomaceous earth : 46%

The ingredients are blended, coarsely hammer-milled and then, air milled to produce particles of active essentially all below 10 microns in diameter

EXAMPLE 7 Emulsifiable concentrate

3-N-methyl-N-3-chloro-4-methoxyphenylaminooxo-acetyl)-2-(4-isopropyl-4-methyl-5-oxo-2 -imidazolin-2-yl)-5-methylpyridine:

10%

chlorobenzene : 84% sorbitan monostearate and polyoxyethylene condensates thereof : 6%

The ingredient are combined and stirred to produce a solution which can be emulsified in water for application

EXAMPLE 8 Dust

3(N-methyl-N-3-fluorophenylaminooxoacetyl)-2-(4-isopropyl-4methyl-5-oxo-2-imidazolin-2 -yl)-5-methylpyridine : 10%

attapulgite : 10%

pyrophylite : 80%

The active ingredient is blended with attapulgite and then passed through a hammer-mill to produce particles substantially all below 200 microns. The ground concentrate is then blended withpowdered pyrophylite until homogeneous.

EXAMPLE 9 Granule

wettable powder of Example : 6%

attapulgite granules : 95%

(U.S.S. 20-40 mesh ; 0.84˜0.4 mm)

A slurry of wettable powder containing 25% solids is sprayed on the surface of attapulgite granules in a double- cone blender. The granules are dried and packaged. 

What is claimed is:
 1. 3-(aminooxoacetyl)-2-(2-imidazolin-2-yl)-pyridine and its salt having the structure of formula (I) ##STR161## wherein, R¹ is C₁ -C₄ alkyl;R² is C₁ -C₄ alkyl, C₃ -C₅ cycloalkyl or C₁ -C₄ alkyl optionally substituted with 1-4 fluorine; R³ is hydrogen, C₁ -C₃ alkyl, C₁ -C₃ alkyl optionally substituted with substituents contained in the following group I, C₂ -C₄ alkenyl or C₂ -C₄ alkynyl; R⁴ is the same as R³ ; or phenyl optionally substituted with 0-3 same or different substituents selected from the substituents contained in group II W is O or S; X is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkoxyalkyl, or halogen, Y, Z are each hydrogen, halogen, C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁ -C₆ alkoxyalkyl, C₁ -C₆ alkylthio, phenoxy, C₁ -C₆ haloalkyl, C₁ -C₆ alkylamino, C₁ -C₆ alkylsulfonyl or phenyl optionally substituted with one C₁ -C₄ alkyl, C₁ -C₄ alkoxy or halogen; A is hydrogen or --COR⁵ (where R⁵ is hydrogen, methyl or CH₂ Cl); when A is hydrogen, tautomeric isomer may exist; Group I contains hydroxy, C₁ -C₆ alkoxy, C₁ -C₆ haloalkoxy, cyano, --CO₂ R⁶ (where R⁶ is hydrogen, C₁ -C₄ alkyl, C₂ -C₄ alkenyl, or C₂ -C₄ alkynyl), C₁ -C₄ alkylthio, C₁ -C₄ alkylsulfonyl, phenylthio, phenylsulfonyl, C₁ -C₄ haloalkylthio, C₃ -C₅ alkenoxy, alkoxy, --NR⁶ R⁷ are each hydrogen, C₁ -C₃ alkyl, C₂ -C₃ alkenyl or C₁ -C₃ alkynyl), phenyl, or phenoxy; Group II contains group I substituents 1-3 halogen, nitro, C₁ -C₆ haloalkyl, C₂ -C₆ alkoxyalkyl, C₁ -C₆ alkyl, C₂ -C₆ alkenyl, C₂ -C₆ alkynyl, C₂ -C₆ alkylthioalkyl, --CO₂ R⁹ (where R⁹ is hydrogen or C₁ -C₄ alkyl), --SO₃ R¹⁰ (where R¹⁰ is hydrogen or C₁ -C₄ alkyl), --SO₂ NR⁶ R⁷, --CONR⁶ R⁷ ()R⁶,R⁷ are the same as above).
 2. The compound according to claim 1 where R¹ is methyl; R² is ethyl or isopropyl; R³ is hydrogen, methyl, ethyl, methoxymethyl, methylthiomethyl, or allyl, R⁴ is C₁ -C₂ alkyl optionally substituted 0-2 substituents selected from 1-3 halogen, hydroxy, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, R⁶ NR⁷ (where R⁶, R⁷, are hydrogen, C₁ -C₄ alkyl, C₂ -C₄ alkenyl, or C₂ -C₅ alkynyl), phenyl, phenoxy, or phenyl optionally substituted with 0-3 same or different substituents selected from substituents contained in the above group II;A is hydrogen; W is O; X is hydrogen, Y is hydrogen, methyl or ethyl; Z is hydrogen, methyl or ethyl.
 3. The compound according to claim 2 where R² is ispropyl; R³ is methyl or CH₂ C₃ ; R⁴ is phenyl substituted with substiuents contained in the above group II; Y is hydrogen, methyl or ethyl.
 4. The compound according to of claim 3 where R³ is phenyl optionally subsituted 0-2 subsitutes selected from methyl, ethyl, propyl, isopropyl, butyl, tertbutyl, cyclohexyl, methoxy, ethothy, isopropoxy, phenoxy, SCH₃, SO₂ CH₃, Cl, Br, F, (CH₃)₂ N and CF₃ ; Y is methyl.
 5. The compound according to claim 1 having said formula(I) of 3-(N-methyl-N-3-fluorophenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2 -yl)-5-methyl-pyridine.,
 6. The compound according to claim 1 having said formula(I) of 3-(N-methyl-N-3-chloro-4-methoxyphenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2 -imidazolin-2-yl)-5-methyl-pyridine.
 7. The compound according to claim 1 having said formula(I) pf 3-(N-methyl-N-3,5-dimethylphenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2 yl)-5-methyl-pyridine.
 8. The compound according to claim 1 having said formula(I) of 3-(N-methyl-4-n-butylphenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2 -yl)-5-methyl-pyridine.
 9. The compound according to claim 1 having said general formula(I) of 3-(N-methyl-N-4-t-butylphenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2 -yl)-5-methyl-pyridine.
 10. The compound according to claim 1 having said formula(I) of 3-(N-methyl-N-4-phenoxyphenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2 -yl)-5-methylpyridine.
 11. The compound according to claim 1 having said general formula(I) of 3-(N-methyl-N-3-chlorophenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2 -yl)-5-methyl-pyridine.
 12. The compound according to claim 1 having said formula(I) of 3-(N-methyl-N-4-cyclohexylphenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2 -yl)-5-methyl-pyridine.
 13. The compound according to claim 1 having said formula(I) of 3-(N-methyl-N-4-dimethylamionophenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2 -yl)-5-methyl-pyridine. methyl-pyridine.
 14. The compound according to claim 1 having said general formula(I) of 3-(N-methyl-N-3-trifluoromethylphenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2 -yl)-5-methyl-pyridine.
 15. The compound according to claim 1 having said formula(I) of 3-(N-methyl-N-3,4-dichlorophenyl-aminooxoacetyl)-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5 -methyl-pyridine.
 16. The compound according to claim 1 having said formula(I) of 3-(N-methyl-N-4-trifluoromethylphenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2 -yl)-5-methyl-pyridine.
 17. The compound according to claim 1 having said formula(I) of 3-(N-methyl-N-3-methylphenyl-aminooxoacetyl)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2 -yl)-5-methyl-pyridine.
 18. A herbicidal composition comprising an effective amount of the compound of claim 1 as active ingredient and a suitable carrier.
 19. The composition according to claim 18, in the form of a wettable powder wherein said composition has the following formula: 45-80 wt percent active ingredient, 20-40 wt percent micro-powder carrier, 2-5 wt percent dispersing agent and 2-5 wt percent non-ionic surfactant.
 20. The composition according to claim 18, in the form of a flowable liquid, wherein said composition has the following formula: 30-50 wt percent active ingredient, 1-3 wt percent gelator, 1-5 wt percent dispersing agent, 0.1-3 wt percent alcohol and 40-60 wt percent water.
 21. The composition according to claim 18, in the form of an emulsified concentrate wherein said composition has the following formula: 5-25 wt percent non-ionic surfactant.
 22. The composition according to claim 18, in a particle form, wherein said composition has the following formula: 3-20 wt percent active ingredient and 80-97 wt percent granular carrier.
 23. A method of using the composition of claim 18, comprising the step of applying the composition to the soil in a ratio of about 0.03-10 kg/ha. 